Process for recovering olefins from mixtures with aluminum alkyls

ABSTRACT

THE SEPARATION OF OLEFIN MATERIALS FROM TRIALKYL ALUMINUM MATERIALS IS ENHANCED BY REACTING SUCH MIXTURES WITH DRY AIR TO CONVERT A PORTION, AT LEAST ABOUT ONE-THIRD, OF ALL TRIALKYL ALUMINUM MOLECULES TO AT LEAST A MONO ALKOXY ALUMINUM SPECIES AND VAPORIZING AT LEAST A PORTION OF THE OLEFINS AT ELEVATED TEMPERATURE. ENHANCED SEPARATION IS OBTAINED AND ISOMERIZATION, DIMERIZATION AND OTHER REACTIONS ARE OTHERWISE CATALYZED BY TRIALKY ALUMINUM MATERIALS AT THE SEPARATION TEMPERATURES ARE MINIMIZED. THE OLEFIN MATERIALS AND TRIALKYL ALUMINUM MATERIALS CAN BE IN LIQUID OR VAPOR PHASES OR COMBINATIONS. GENERALLY SPEAKING, THE OLEFINS ARE THEN RECOVERED AS A VAPOR AND THE ALUMINUM MATERIALS AS LIQUID.

Jan. 19, 1971 1 K PRESSWQOD ETAL 3p55736 PROCESSl FOR RECOVERING OLEFINS FROM MIXTURES WITH ALUMINUM ALKYLS Original Filed March 16. 196'?` Nm wZEmI E344 IEP KQ LO United States Patent O1 3,557,236 Patented Jan. 19, 1971 iice- 3,557,236 PROCESS FOR RECOVERING OLEFINS FROM MIXTURES WITH ALUMINUM ALKYLS John K. Presswood and Walter E. Foster, Baton Rouge, La., assignors to Ethyl Corporation, New York, N Y., a corporation of Virginia Application Mar. 16, 1967, Ser. No. 634,015, now Patent No. 3,400,170, which is a continuation-in-part of abandoned application Ser. No. 198,113, May 28, 1962. This application Mar. 18, 1968, Ser. No. 713,654

Int. Cl. C07c 11/02 U.S. Cl. 260-677 9 Claims ABSTRACT OF THE DISCLOSURE The separation of olefin materials from trialkyl aluminum materials is enhanced by reacting such mixtures 'with dry air to convert a portion, at least about one-third, of all trialkyl aluminum molecules to at least a mono alkoxy aluminum species and vaporizing at least a portion of the oleiins at elevated temperature. Enhanced separation is obtained and isomerization, dimerization and other reactions usually otherwise catalyzed by trialkyl aluminum materials at the separation temperatures are minimized. The olefin materials and trialkyl aluminum materials can be in liquid or vapor phases or combinations. Generally speaking, the olefins are then recovered as a vapor and the aluminum materials as liquid.

This application is a division of application Ser. No. 634,015, filed Mar. 16, 1967, which in turn is a continuation-in-part of application Ser. No. 198,113 filed May 28, 1962, now abandoned.

This invention relates to an improvement in the manufacture of relatively low -molecular weight alpha olen products. More particularly, the invention relates toI an improved operating procedure whereby olefin hydrocarbin materials are not degraded during recovery operations.

Of recent years, considerable interest has developed in the manufacture of alpha olefin hydrocarbons of the normally liquid molecular weight range, these materials being desired for a variety of purposes in further utilization. By the term low molecular weight alpha olefins is meant, herein, the primary olefins of from six to about twenty carbon atom content in the molecule, with particular interest being exhibited for the range of decene to octadecene alpha oleiins, and an even more particular interest being displayed for the fraction including dodecene, tetradecene and hexadecene.

One highly attractive potential method of synthesizing olefins of the above described character, from ethylene, involves the use of trialkyl aluminum materials, either as catalysts, or as a stoichiometric reagent. A catalytic polymerization of ethylene to produce olefins in the molceular weight range described is characterized by the truly catalytic function of the trialkyl aluminum components. By this is meant that a large number of moles of olefins, generally, is synthesized relative to the quantity of catalyst present in a reaction zone. The catalytic method has considerable appeal, but its acceptance and utilization has not been realized because of certain weaknesses hereafter mentioned.

The other major approach to making the alpha olefins involves the stoichiometric chain growth, of a plurality of ethylene molecules on each alkyl group of a trialkyl aluminum startin-g material, followed by a so-called displacement process, wherein a long alkyl group is released by the trialkyl aluminum compound as an olefin, and a new alkyl group of shortened length is established, whereby trialkyl components suitable for recycling to the chain growth operation are engendered.

In both of the foregoing types of processes, a particular objective has been to attain an alpha olefin product mixture having a high, consistent, and reproducible content of the vinyl olens. By vinyl olefins is meant the normal unbranched alpha olefns, whereas the usual undesired impurities are vinylidene type olefins, wherein a branched alkyl moiety is attached at the two carbon of the alpha olefin molecule. Another highly undesirable impurity in the olefins engendered by a catalytic process are internal olefins, especially the transisomers. In general, it is desired to obtain olefin products for marketing or for further use, having a vinyl olefin purity of at least about weight percent in a relatively narrow cut fraction, and preferably of the order of about weight percent.

A further problem arises, however, in the fact that the alkyl aluminum components employed as the catalyst must, obviously, be separated from the mixture of olelins which is the major portion of a reactor efiiuent. In carrying out a catalytic ethylene polymerization with a trialkyl aluminum catalyst, the alkyl groups thereof tend to themselves be increased in chain length, and, in fact, appear to exhibit a distribution of chain lengths roughly corresponding to the distribution of the oleins made.

An obvious mode of separating trialkyl aluminum constituents of a reactor effluent from the other components thereof, is to carry out a fractional distillation. It has been discovered, however, that at the temperatures of operation necessary to achieve a fractionation, i.e., in the reboiler of a fractionating column, the temperatures necessarily used, in conjunction with the presence of the trialkyl aluminum catalyst residues exhibit a pronounced deleterious effect. In other words, the very fact of separating olefin product streams, or by-prouct streams, from trialkyl aluminum constitutents of a reactor effluent, in itself, using the usual approach, will result in a `quality decrease for the final alpha oleins engendered. This quality decrease is exhibited as the appearance of internal olens, of various positions in a multi-carbon molecule, the trans-isomers being by far the predominant internal olefin isomer, but the cisisomer also being found. As said internal isomers are not desirable for the majority of uses for which the vinyl olelins are desired, they constitute a highly undesirable impurity. In addition to the internal olens which are formed, it is also lfound that attempts to fractionate result in a substantial increase in the amount of vinylidene alpha olefin impurities. The precise reaction mechanisms are not known which result in internal olefin or vinylidene olefin impurities. However, it is definitely established that the presence of trialkyl aluminum, when the reactor effluent is subject to distillation conditions, results in the formation of the above undesired impurities.

Among the end uses to which the desired vinyl olefin fraction can be provided are feed stocks for the formation of alkyl aromatic compounds, which find utility as solvents or as starting materials for the preparation of synthetic detergents. The vinyl olefins can also be used to manufacture normal alcohols by the anti-Markownikoff addition of hydrogen halides and the subsequent hydrolysis to yield a normal monohydric compound. The vinyl olens are also subject to pyrolytic dehydrogenation or catalytic dehydrogenation to yield diolefins which are suitable as startin-g materials for formation of polymers or copolymers with other monomers, or as starting materials for the preparation of dihydoxy compounds.

As mentioned above, however, considerable difficuty has been encountered in providing a process yielding the desired product streams free of the non-vinyl isomers because of the recovery problem described.

An object of the present invention is, then, to provide an improvement in a process of making vinyl olefins by the alkyl aluminum-catalyzed polymerization of ethylene, said improvement substantially eliminating the formation of non-vinyl isomers in the final recovered product. A more particular object is to provide such an improvement, in a process including a catalytic polymerization operation and fractional recovery operations, wherein the recovery operations are at conditions which substantially promote or favor the formation of non-vinyl olen isomers from the alpha olefins actually synthesized in the catalytic polymerization operation per se. Yet another object of the preferred embodiment of the improvement is to provide a method of preventing isomer formation during fractionation recovery operations, wherein the improvement does not necessitate the introduction of extraneous and undesirable materials.

Another object of the present invention is to provide improved separation of olefins and trialkyl aluminum materials where either or both are in the vapor phase and additionally wherein separation from trialkyl aluminum materials is enhanced for non-vinyl olefins.

Other and other further features of the present invention will become apparent upon careful consideration of the following description and drawings wherein:

FIG. l is a fiow sheet of a plant installation embodying features of the present invention.

FIG. 2 shows additional details of fractionator 31 of FIG. l useful in exemplifying various features of the present invention.

In its simplest expression the present invention is illustrated in FIG. l in the step of treating a stream in line 24 containing olefins and trialkyl aluminum materials from line 22 with a reactant from line 23 to convert the trialkyl aluminum constituents to components having on the average at least one and up to three alkoxide groups per molecule and the separation of olefins in fractionator 31. Thus, the trialkyl aluminum materials are converted to dialkyl aluminum alkoxide, alkyl aluminum dialkoxide, or aluminum trialkoxide components, or mixtures thereof. Thus converted, it is found that separation operations, even at rigorous conditions, can be readily carried out yielding non-degraded olefins in line 32 and alkoxy aluminum alkyl species in line 33.

In carrying out the process, it is frequently desirable to accomplish the above conversion without introducing inert gaseous components. Thus, although air can be used to accomplish the oxidation, gaseous oxygen is preferred. An even more beneficial class of embodiments of the invention involves the use of a high-alkoxide aluminum component, to interreact with the trialkyl aluminum constituent of the stream and provide the desired conversion by a completely liquid phase reaction treatment. The treatment provides a conversion of the trialkyl aluminum constituents of the process stream to compounds averaging at least one alkoxide group in each molecule. In the course of this treatment, the higher aluminum alkoxide components lose a portion of their alkoxide groups, which are replaced by alkyl groups. The compounds thus derived necessarily contain at least one alkoxide group per mole; hence, in these embodiments, the recycled high-alkoxide aluminum component is apportioned to provide excess alkoxide groups in quantity at least sufficient to provide one alkoxide group per mole of trialkyl aluminum constituent in the stream being treated.

In certain embodiments the so-treated stream can then be safely again subjected to conditions which would otherwise result in adverse effects due to the presence of trialkyl aluminum materials. The alkyl aluminum alkoxide components can be safely concentrated by a plurality of fractionations in a stream including olefins of higher molecular weight than normally desired. This stream is then subjected to oxidation with an oxidizing gas to convert the entire alkyl aluminum alkoxide components present to high-alkoxide constituents. In brief, the alkyl aluminum alkoxide constituents are oxidized further to the extent of, usually, averaging at least two alkoxide groups per molecule, and up to the corresponding aluminum trialkoxides. The thus oxidized stream is returned in part to the above-mentioned treating step of the feed stream to the fractionation section. The portion not returned can be reacted with an aqueous agent to convert the non-recycled high-alkoxide components to alcohols and an aluminum inorganic compound. Customarily, the heavy olefin constituent present in such a portion of the stream are removed prior to said hydrolysis, but this is not essential.

The present alkoxide treatment to facilitate the recovery of olefins from mixtures thereof with trialkyl aluminum materials has extremely useful application in several ways. In addition to liquid phase situations, either or both the olefins and trialkyl aluminum materials can be in the vapor phase or in mixtures of partially liquid, partially vapor phase condition. In addition to inactivating the trialkyl aluminum materials as catalysts of olefin alteration, the treatment has a very significant secondary benefit that in many instances can be more soughtafter than the inactivation per se, This secondary benefit arises through the vapor pressure or boiling point differences between trialkyl aluminum materials and the corresponding dialkyl aluminum monoalkoxide materials.

To exemplify the foregoing, reference is now made to FIG. 2, particularly with regard to fractionator 31. Incompletely reacted trialkyl aluminum materials entering this vessel are frequently vaporized or atomized in the reboiler thereof or on the way to the reboiler, passing upward as vapor and as droplets. This material upon encountering incoming dior trialkoxy aluminum material supplied through line 24 will react to be converted to a partial alkoxy species. Thus'the reactions in 31 below line 24 (in portion 31C) include not only a continuing reaction between the alkyls and alkoxides of the incoming stream from line 24 in liquid stream form but also include a liquid phase-vapor phase contacting between the alkoxides and trialkyl aluminum material that ends to pass overhead in 31. Such reaction traps the overheadgoing material as a low vapor pressure liquid alkoxide species which then passes downward in liquid form to exit through line 33.

So effective is this treatment that it is beneficial in some instances to supply an additional dior trialkoxide stream or mixture to fractionator 31 above the point of entry of line 24 as through line 24a using conventional plates or packing 31a between line 24a and line 24, to react with trialkyl aluminum vapor and droplets that pass upward in fractionator 31 above the feed line 24. This provides a very pure'foverhead olefin stream having extremely small content. of aluminum materials, typically 0.1 percent by weight, or less.

In many instances where the recovery of olefins from trialkyl aluminum materials is desired one may not wish to convert all the trialkyl aluminum materials to an alkoxide species but yet may wish to obtain the excellent separation of vaporized and entrained trialkyl aluminum material from the (upper) portion of fractionator 31 above the feed line 24 as mentioned in the preceding paragraph. Such may be exemplified in flash separations where the contact time in the lower portion of the fractionator 31C below line 24 is so short or the temperature so low that there is not a great deal of concern over catalyzed degradation in that region, but where trace quantities of trialkyl aluminum materials passing overhead in vapor or entrainment form together with the olefins are very much undesired as where the olefins are later fractionated and thereby heated sufficiently to cause degradation.

In this instance it is frequently advantageous with a feed of dior trialkoxide through line 24a above contacting section 31a to place a partition or collector 3111 across the fractionator 31 above line 24 which permits the free fiow upward at that point of vaporized and entrained oleiins and trialkyl aluminum material into the upper plate or packed section 31a but which collects the liquid downflow of alkoxide materials and diverts it so that it does not mix with the liquid material in the fractionator 31 below the feed line 24. Such a partition typicalunwanted internal and vinylidene olefin isomers. In contrast, when similar concentrations of aluminum compounds, having from slightly above one to three alkoxide groups, per atom of aluminum, were provided, and the heating operations were carried out, the formation of ly has a form of a transverse plate with a central stack the internal and vinylidene isomers was substantially elimhaving over it an umbrella arrangement to shed liquid but inated.

permitting free upward passage of vapor. Liquid collect- As previously described, the process is applied to ing above the plate is then withdrawn through line 33a streams having not only olen product components in a placed just above the plate. The result of this is (l) a very desired molecular weight range, but also non-desired olepure overhead olefin stream in line 32 having extremely ns, and also trialkyl aluminum constituents present in small contamination by aluminum materials, (2) a bOtthe effluent stream. To illustrate the difficulty encountered toms trialkyl aluminum stream in line 33 with little or no with such a stream, and in the fractionation of such a alkoxide content and (3) a side stream of alkoxy alumistream, the following example is illustrative.

num species in line 33a. Although the second and third l5 Ethylene was polymerized by subjecting to elevated streams may permissively contain olelins, the presence or temperature and pressure in the presence of a trialkyl absence of such is not essential. aluminum catalyst, initially charged as triethylaluminum.

In further extension of the foregoing, the volatility After termination of the reaction, the reactor products aspects of the treatment with dior trialkoxide (alumihad the following approximate composition; on an aluminum) species of mixtures containing trialkyl aluminum num alkyl free basis: materials is so startling and effective as to make such desirable to facilitate recovery of pure olens even where Fraction; Weight percent degradation of the oleiins is not a prime consideration. @1 8 2() Thus although the main force of the present invention is C10 14 3() directed toward separations which preserve vinyl olens C16 and up 50 without degradation, such as by isomerization or dimerization; the invention also is highly valuable in separations In addition to the olens, the reactor products included a where the olefins are not predominantly vinyl, typically high proportion of trialkyl aluminum components, the being in large part internal or vinylidene types or mixtures alkyl groups corresponding approximately in distribution of several or all types. to the olen fractions.

To illustrate the principle of the invention, the follow- 'Ihe foregoing reactor eiuent mixture was subjected ing examples show the eifect of heat on formation of to distillation under a vacuum of about 10 millimeters of non-vinyl olefin isomers, starting with aparticular reagent mercury. The temperature of the overhead during the grade olefin, such as is found in the eflluent mixture from major portion of this distillation was about 160 C., the a catalytic polymerization operation. In these series of D pot temperature being about 200 C. The distillate was examples, l-eicosene was employed, and analysis of this separated into cuts, the second cut having oleiins coneicosene showed that, as received, it contained about eight taining l0 to 14 carbon atoms. Analysis of this cut by weight percent of the trans-internal isomers. This parinfrared absorption showed a content of at least about ticular sample did not contain any vinylidene olens. A 4U 80 weight percent trans-internal oleiins, approximately charge of 110 grams of the olen was employed in each l0 Weight percent of vinyl olens, and 10 weight percent' of the operations for which the results are tabulated below. vinylidene olens. In contrast, infrared analysis of the The operation included charging to a flask provided With a reactor effluent charged showed that the olens only conthermometer, stirrer, condenser and nitrogen blanket systained about two or three weight percent of the transtem. In all cases the specimen was purged of oxygen by internal olefins. From the above operation, it is seen that passing nitrogen over the charge, and then the specimen the distillation of the reactor effluent is utterly impractical, was heated, with stirring, to 260 C. Samples were re- 'under normal circumstances, because of the great dismoved at 15, 30 and 60 minute intervals, and then appearance of vinyl Olens from the olen portion of analyzed by infrared absorption to determine the change the stream, thus destroying the utility of the product in composition if any. In most of the operations, alumigenerated. num compounds were added in concentrations correspond- The fOllOWmg example lllustrates a similar operation ing to an aluminum mem concentration of 0,2 Weight with a treatment of the reactor efuent according to the percent, except in one noted instance. present Pf0CeSS- Weight Weight;

Heating Temperpercent percent time, atuie, transvinylidene Example Additive minutes C. eicosene elin 1113111223: itiv'iaaarasit'.; (l "auf 431i N 3 3o 250 54 23.1 4 60 220 65.5 25.2 5 15 260 8.4 None so 270 7.0 7 G0 270 6.2 8 15 260 8.7 n 30 260 8.o

so 260 8.3 11 Reaction product of triethyl 15 260 8.1 None aluminum and aluminum triisoproposid equimolal 12 do so 260 s. 0 13 do 60 260 8.3

2 In the triethyl aluminum runs, the triethyl aluminum Was provided in concentrations oi 0.3 weight percent, on the aluminum basis.

From the foregoing data, it is seen that exposure of the pure olefin to a temperature of the order of 260, and in the presence of minor quantities of trialkyl alumi- EXAMPLE 14 In this operation ethylene was again subjected to elevated temperature and pressure in the presence of triethyl num, resulted in a profound and rapid increase in the aluminum, initially, and also in the presence of a moderate quantity of an inert aromatic hydrocarbon diluent, toluene. After reaction, the reactor efiiuent contained approximately 30 weight percent trialkyl aluminum components and about 70 percent olefins, ignoring the toluene diluent. The olefins had a distribution approximately as follows:

Chain length range: Weight percent 02:10 25 C13-13 25 C1; and higher 50 Analysis of the olefin content of the reactor effiuent, by infrared absorption, showed the sample contained less than three weight percent internal olefins, and about sixteen weight percent, overall, of the vinylidene or beta branched olefins, the balance being the desired vinyl isomers.

The sample was warmed to about 40 C. and maintained at this temperature while dry air was passed into the sample through a glass frit, for a period of approximately 30 minutes. This treatment resulted in the conversion of a portion, of at least about one-third, of the alkyl groups of the trialkyl aluminum constituents, to the corresponding alkoxide groups. The so-treated mixture was then charged to a distillation fiask and distilled, the first cut being an olefin fraction of from four to eight carbon olefins. The next fraction was a decene cut and then a twelve to sixteen carbon olefin fraction, leaving as residue a fraction including olefins of 18 carbon atoms or greater and the aluminum alkyls. The conditions of operation in collecting the C12 16 fraction were about 160 C. overhead temperature at about 10 millimeters distillation pressure, the pot temperature again being up to 200 C.

Analysis of the C12 16 fraction by vapor phase chromatography showed no increase in vinylidene content or any internal olefin content, thus showing that the distillation could be effected, after the treatment with the oxidizing gas, with no increase in proportion of undesired olefins.

As previously described, in the most highly preferred form of the present invention, the treatment of the polymerization reactor effluent, or the portion fed to the fractionation section, is accomplished by reacting with a liquid recycle stream including a process-generated alurninum higher alkoxide containing stream. This highly preferred embodiment is illustrated in connection with FIG. l to which attention is directed. The principal apparatus units include a polymerization reactor 11, an initial flash chamber 21, fractionating columns 31, 41, a final fractionator 51, and an oxidation reactor 61. The polymerization reactor 11 is fed by an ethylene line 16, the total reactor effluent thereafter being passed by a line to an ethylene flash chamber 2l. The transfer line 22 from the ethylene flash chamber is joined by a recycle line 23, forming the feed line 24 to the first fractionator 31. In the several fractionators 31, 41, 51, the alkyl aluminum alkoxide constituents present remain in the bottoms streams, these materials being of much less volatility than the olefins present. Thus, a bottoms line 53 from a final flash fractionator 51 contains virtually all the alkyl aluminum alkoxide constituents, and this relatively small stream is fed to an oxidizing reactor 61 through a bottoms line 53.

The oxidizing reactor 61 is fed with an oxidizing gas through line 62, the treated material being discharged through a bottoms line 64.

To illustrate a working example of a highly preferred embodiment in the process installation above described, the following is typical.

EXAMPLE 15 In this operation ethylene and recycled ethylene are fed to the polymerization reactor 11 through the ethylene gross feed line 16, along with catalysts, which in this instance is triethyl aluminum, supplied through line 14. The ethylene is subjected to catalytic polymerization in the reactor 11, and the reactor efiiuent includes unreacted ethylene, olefins generated by the process, and trialkyl aluminum components, the alkyl groups thereof having chain length distributions roughly approximating the distribution of the olefins in the reactor effluent stream 1S.

The reactor efiiuent stream is discharged to the ash chamber 21 in which Virtually all of the excess ethylene is allowed to vaporize, the chamber being maintained at a lower pressure than the reactor 11. As a result, the effluent stream from the fiash chamber 21, passed through line 22 has, in a typical operation, the following approximate composition:

Component: Wt. percent Olefins:

Up to Cl-D incl 65 Cl-g and higher l1 Trialkyl aluminums-RAl (R=alkyls corresponding to olefins, averaging R=C8H11) 1.5-2.0

It will be understood that the trialkyl aluminum constituents present include a random mixture of individual components, the alkyl groups thereof varying according to, approximately, the distribution of the olefins in the eiuent. Further, when the polymerization reaction is carried out properly, the vinyl olefin content of the stream olens is of the order of about or greater mole percent. The principal impurity is vinylidene olefins, particularly in the higher molecular weight range of the olefins, with only minor quantities or trace quantities of trans-internal olefins and virtually no cis-internal olefins.

Fed to the transfer line 22 through line 23 is the treating stream including as a principal component thereof an aluminum alkoxide compound having greater than one alkoxide group per atom of aluminum present. Generally, the aluminum alkoxide constituent of this treating stream contains at least two alkoxide groups, and in some instances, the reagent will be a mixture of aluminum trialkoxide. In this instance, the recycled treating stream fed through line 23 contains alkyl aluminum dialkoxides, and is provided in proportions giving at least one mole of such higher alkoxide per mole of the trialkyl aluminum constituents in the stream to be treated. When the treating stream, on the other hand, contains aluminum trialkoxide, the necessary amount of this component is at least one-half mole per mole of trialkyl aluminum.

The treating stream and the reactor effluent promptly react in the feed line 24. The reaction actually implemented is a redistribution of the trialkyl aluminum constituents of the reactor efiiuent with the aluminum alkoxide constituents of the treating stream supplied through line 23. In the present instance, the aluminum alkoxide constituent of the treating stream 23 is an alkyl aluminum dialkoxide, and the treating reaction actually carried out can be represented as follows:

In the foregoing equation, R represents the same and different alkyl groups, corresponding generally to olens in the reactor efiiuent portion in line 22.

The streams are then fractionated in the several fractionators and the desired olefin cuts are isolated. Because of the treatment accomplished, by the above indicated reaction in line 24 and in feeding to the first column 31, the adverse effect of the orginal trialkyl aluminum constituents is substantially entirely avoided, despite the drastic conditions necessarily employed in the fractionators. The first fractionator 31 separates out an overhead stream, discharged through line 32, of olefins of 4 to 10 carbon atoms inclusive, these being transferred to other consuming processes. The bottoms stream in bottoms line 33 includes olens of 12 and more carbon atoms as Well as the alkyl aluminum alkoxides. Typical operating conditions for the first fractionator are a bottoms temperature of 230 C. and an operating pressure of one atmosphere.

The second fractionator 41 provides an overhead consisting of the desired product stream, in this instance high vinyl olefins of 12 to 16 carbon atoms, inc. This product stream is virtually devoid of any increase in amount of non-vinyl olefins, containing only the small proportions initially present in the feed to the recovery section in line 22. The fractionator operates at a reduced pressure of the order of about 100 millimeters of mercury, with a bottoms temperature of from 230 to 240 C. Leaving the second -fractionator 41 is the bottoms stream, including the dialkyl aluminum alkoxide, resulting from the reaction accomplished by the return treating stream 23 above mentioned. Also in the bottoms stream are the lhigher-than-desired olens, in this instance including aolens of 18 up to about 30 carbon atoms, the relative amounts decreasing rapidly with the increase in chain length. This stream is then passed to the final ash frac- '.tionator 51, for vaporization of at least a portion of such heavy olens, these being discharged through line 52. The bottoms, still including the alkyl aluminum alkoxide constituents and some of the high molecular Weight olens, is transferred by line 53 to the oxidation reactor 61.

In the oxidizing reactor 61, a reaction is conducted with oxidizing gas provided through line 62. Preferably an oxygen rich stream is employed to facilitate the oxidation, but air is also quite suitable. Oxidation temperatures of the order of up to about 100 C. are employed, and any inerts and vaporized components are discharged through line 63. The oxidation converts the dialkyl aluminum dialkoxide, or into constituents having an average of from about 1.8 to 2.2 alkoxide group per aluminum atom. The thus treated stream is discharged through line 64, and split into approximately equal portions, one portion being returned through line 23 for the treating step already mentioned, and the other portion being passed through line 65. The discharged stream can be subjected to hydrolysis with an aqueous reagent, which converts the alkoxide groups to the corresponding alcohols, which can be recovered for use if desired. Alkyl groups, present in the alkyl aluminum alkoxide components, are converted to the corresponding alkane hydrocarbons.

From the foregoing description and examples, it will be apparent that many variations of the process can be implemented without departing from the scope of the present invention. For example, although the invention is most frequently applicable as an improvement in the production of vinyl olefins of l2 to 16, inc., carbon atoms, in many instances, different product fractions are desired. Thus, the most desired fraction can be 8-12 carbon olens, 10-18, or 14 to 20, inc. When such products are the most desired, the conditions in the polymerization reactor are suitably adjusted, and, of course, the design of and/ or the operations of the fractionating columns are altered accordingly.

Typical operating conditions in the polymerization reactor are 180 to 200 C. and a pressure of 2500-4000 pounds per square inch. Ethylene is almost invariably fed in substantial excess, usually of at least 50 percent of the quantity reacted. The trialkyl aluminum catalyst is provided, normally, in the proportions of 1 to 3 lb. per 100 lb. of the net ethylene reacted, expressing the trialkyl aluminum.

The precise conditions of the treating step, provided prior to the fractionation operations in all forms of the invention, are not highly critical. Normally, the existent process temperatures of the stream are quite suthcient to permit the necessary reaction to occur in the space of several minutes.

As already described, when the treatment is carried out with air, the inert gas introduced in the system must necessarily be eliminated, for example by a pressure controlled venting. As such venting also releases some hydrocarbons, it is preferred to use concentrated oxygen, and in proportions such that the oxygen is substantially completely consumed.

In the embodiments wherein the treating reagents are gases, it is important to provide good dispersion of the gas, to assure good contact with the liquid stream being treated. Various known devices can be readily used for this purpose. For example, the oxidizing gas can be fed through a glass frit, or vigorous mechanical agitation can be supplied. In many instances, the natural turbulence provided in passing through a process line as in line 24 of the figure, is suicient.

In the most highly preferred embodiments, illustrated by Example 15, wherein the treatment step involves the novel interreaction of the trialkyl aluminum components with the higher alkoxide content aluminum alkoxide components, similar latitude exists. A particular benefit of such embodiments is the fact that the treatment is an entirely liquid phase reaction, the criteria of contacting is that good liquid-liquid mixing should be provided. Again, in numerous cases, mixing by turbulent ow through a process conduit is quite satisfactory. In other instances, bafes or agitation elements are used to advantage.

With respect to the final conversion of the low alkoxide components, to a higher alkoxide material, this operation is also relatively straightforward. As this step is carried out when the alkyl aluminum alkoxide components are concentrated in the non-desired, heavy olefin components, the presence of inert gas is not particularly disadvantageous. However, when it is desired to convert the alkyl aluminum alkoxide components completely to aluminum trialkoxides, it is desirable to provide pure oxygen, vigorous agitation, and temperatures of the order of 50-70 C.

The analytical procedures employed for control are relatively simple. Thus, in treating the stream containing trialkyl aluminum constituents prior to fractionation, it is necessary to know the concentration of aluminum components, which can be considered as entirely trialkyl constituents. To determine the degree of conversison of alkyl groups to alkoxide groups, hydrolysis of a sample, and measurement by infrared techniques of the amount of alkane hydrocarbons released, and of the alcohols, will show the average proportion of alkoxide groups in the aluminum constituents present. Once steady state conditions are established in a continuous process, control analyses can be performed at widely spaced intervals.

EXAMPLE 16 With reference to FIG. 2, the feed components in line 24 include on a mol basis, trialkyl aluminum mixture and olefins predominating in similar components from about C10 to C16, the mixture including about 20 wt. percent trialkyl aluminum, 50 wt. percent vinyl olens, 20 Wt. percent internal olefins and 10 wt. percent vinylidene olefins. Also in the feed to line 24 is included trialkoxy aluminum material whose alkoxy groups are of about the same distribution as to carbon atoms per groups as are the alkyl groups of the trialkyl aluminum material, the alkoxide aluminum being fed in a ratio of about 10 percent excess above a 1:1 stoichiometric ratio of alkoxide groups to total aluminum molecules present considering an aluminum molecule to be that equivalent to a representation in Al(R)3, Al(OR)3, R2Al(OR), and RAl(OR)2.

The fractionator 31 is primarily a flash chamber in the sense that contact time therein is short with no plates or packing in the lower portion 31C and a major portion of the olens in the feed is rapidly converted to vapor near the point of entry of line 24 into fractionator 31. Alkoxide-alkyl exchange reactions are virtually complete on entry of feed material to fractionator 31 so that all aluminum molecules contain at that point at least one alkoxy group. Fractionator 31 operates at a bottoms temperature of about 400 F., which is also the temperature of the ashed feed, and at a pressure of 50 mm. Hg absolute. The components 24a, 31a, 31b and 33a are not used as alkoxide manipulation devices however 31a is a simple disengaging region to separate entrained liquid materials from the olefin vapors passing upward. Extremely pure olens with less than 0.001 wt. percent aluminum by analysis are recovered in line 32 and alkoxides with some olens are withdrawn at 33. The olens in 33 are usually less than 50 percent by weight of that stream which corresponds to the removal in line 32 of about 75 percent of the olens fed.

EXAMPLE 17 `Example 16 is repeated with incomplete exchange in the feed prior to entry to fractionator 31. Portion 31C has several plates to extend contact time. Similar results are obtained with the exchange reactions continuing into fractionator 31. A higher content of aluminum materials in the product of line 32 is noted in comparison to Example 16.

EXAMPLE 18 Examples 16 and 17 are repeated with other olen/ alkyl weight ratios and distributions as to molecular weight of alkyl groups and olens, and as to kinds of olens including mixtures wherein the olefns are predominantly internal, predominantly vinylidene, exclusively internal, and exclusively vinylidene. Similar results are obtained.

EXAMPLE 19 Examples 16 and 17, combined with the variations of Example 18, are repeated wherein the trialkyl aluminum materials and the olens are fed through line 24 and the alkoxide materials are fed through line 24a. The components 24a, 31a, 31b and 33a are used for alkoxide manipulations. Portions 31C of fractionator 31 is typically open without plates or packing as in Example 16. The bottoms temperature and that of the flashed feed at 24 is 320 F. The pressure is 50 mm. Hg absolute. Trialkyl aluminum materials with about 65 percent by weight olens are withdrawn at 33 corresponding to removal of 50 percent of the olens fed. The olefins flash near line 24 entry point passing upward in fractionator 31 carrying with them a minor portion, about 0.1 wt. percent trialkyl aluminum materials in vapor-droplet form. The amount of trialkoxy aluminum material fed at 24a is about 100 percent above the stoichiometric ratio as in Example 16;

however, it is determined on the basis of only the aluminum passing upward in 31 above line 24, not on the total aluminum in line 24. The alkoxide fed is diluted with olefins corresponding to those present in the system in a wt. ratio of about /1 (olefin-alkoxide) to increase liquid L An alkoxy-alkyl aluminum species is obtained at line 33a which for example may then be completely oxidized, and hydrolyzed to yield alcohols. The olens may be processed as by fractionation into cuts using high temperatures without degradation, selected cuts being fed to displacement operations. The trialkyl aluminum materials at 33 may be used in typical reactions for such, for example, displacement.

We claim:

1. A process for the separation of alpha oleins of high vinyl olefin content from a mixture with trialkyl aluminum components which comprises:

treating said mixture with dry air to convert a portion,

of at least about one third, of the alkyl groups of the trialkyl aluminum constituents, to the corresponding alkoxide groups; and

vaporizing at least a portion of the olens from said treated mixture, said vaporizing being at an elevated temperature at which positional and structural degradation of the olens could occur if trialkyl aluminum components were present.

2. The process of claim 1 wherein said olens contain no more than 20 carbon atoms in the molecule.

3. The process of claim 1 wherein the olefin-aluminum alkyl mixtures are predominantly olens.

4. The process of claim 1 wherein the olefin-aluminum alkyl mixtures are from about to about 98.5 wt. percent olefins and from about 1.5 to about 30 wt. percent trialkyl aluminum.

5. The process of claim 1 wherein the olefin-aluminum alkyl mixtures are from about 98 to about 98.5 wt. percent trialkyl aluminum.

6. The process of claim 1 wherein the olefin-aluminum alkyl mixtures are about 70 wt. percent olefins and about 30 percent trialkyl aluminum.

7. The process of claim 1 wherein the olen-aluminum alkyl mixtures are derived from a catalytic polymerization of ethylene.

8. The process of claim 1 wherein the olefin-aluminum alkyl mixtures are derived from a stoichiometric chain growth trialkyl aluminum process.

9. In a process in which a mixture of alpha olens and trialkyl aluminum components are subjected to heating with resultant degradation of the alpha olens to nonvinyl olens, the improvement comprising avoiding said degradation by treating said mixture with dry air to convert a portion, of at least about one third, of the alkyl groups of the trialkyl aluminum constituents, to the corresponding alkoxide groups prior to said heating.

References Cited UNITED STATES PATENTS 3,070,616 12/1962 Flanagan 260-448 3,400,170 9/1968 Presswood et al. 260-677 3,309,416 3/1967 Poe et al. 260-683.15D 3,217,058 11/1965 Hunt 260-682 DELBERT E. GANTZ, Primary Examiner I. M. NELSON, Assistant Examiner Pfl-050 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 5,557,256 Dated January 19: 197:

Inventor(s) John K. Presswood et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column l, line 38, reads nhydrocarbin", should read h3 carbon line 56, reads "molceular", should read moi lar Column 2, line 68, reads "difficuty", should read difficulty Column il, line 59, reads l'that ends to", should read that tends to Column 5, Example ll, reads "triisopropos id", should read triisc propoxide Column 9, line 69, reads "aluminum. shot read aluminum as triethyl aluminum. Column l2, line 52, before "triaikyi" add olefins and from about 1.5 to about 5.0 wt. percent Signed and sealed this 15th day of June 1971.

(SEAL) Attest:

EDWARD M.FLETGHER,J'R. WILLIAM E. SGHUYLER, .l Attesting Officer Commissioner' of Patent 

